Lactam-functionalized polymer, compositions  and applications thereof

ABSTRACT

A lactam-functionalized polymer is disclosed. The lactam-functionalized polymer includes lactam-functionalized polyacetal polyether, polyhemiaminal polyether or polyaminal polyether. The applications of the lactam-functionalized polymer are also disclosed.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application claims the benefit under 35 U.S.C. 119 (e) ofU.S. Provisional Patent Application Ser. No. 62/357,442, filed on Jul.1, 2016, the entire content of which is hereby expressly incorporatedherein by reference.

BACKGROUND OF THE INVENTION 1. Field of the Disclosed and ClaimedInventive Concepts

The presently disclosed process(es), procedure(s), method(s),product(s), result(s), and/or concept(s) (collectively referred tohereinafter as the “present disclosure”) relates generally to alactam-functionalized polymer comprising a polymer backbone and at leastone lactam moiety attached to the polymer backbone. In particular, thepolymer backbone can be polyacetal polyether, polyhemiaminal polyether,or polyaminal polyether. Additionally, the present disclosure relatesgenerally to compositions comprising the lactam-functionalized polymersand applications thereof in various industrial areas such as coatings.

2. Background and Applicable Aspects of the Presently Disclosed andClaimed Inventive Concept(s)

Water-soluble polymers (also commonly referred to as “thickeners” or“rheology modifiers”) are widely used in many industrial water-bornesystems as additives to modify their flow behavior. Thickeners increaseand maintain viscosity at required levels under specified processingconditions and end use situations. Thickeners are useful, for example,in decorative and protective coatings, paper coatings, cosmetics andpersonal care products, detergents, pharmaceuticals, adhesives andsealants, agricultural formulations, and petroleum drilling fluids.

One such highly filled aqueous system where the thickener is used in adecorative and protective coating is latex paint, which is composed of adispersion of polymeric latex, pigments, clays, and other additives inwater.

Thickeners can be materials that are either naturally existing orsynthetically manufactured. Natural thickeners, for example, can includecasein, alginates, gum tragacanth, guar, xanthan gum, locust and beangum. Typical examples of naturally derived thickeners can includecellulose ethers derived from celluloses, such as hydroxyethyl cellulose(HEC), hydroxypropyl cellulose (HPC), and carboxymethyl cellulose (CMC).These natural and naturally derived products (hereinafter called“natural products”) vary in their thickening efficiency. One of thedrawbacks of the naturally based thickeners is that they are subject tomicrobial attack and hence, addition of antimicrobial agents to theformulation is required. Synthetic thickeners include various acrylicpolymers, alkylene oxide polymers, amide polymers, and maleic anhydridepolymers. These synthetic thickeners can be either homopolymers orcopolymers. The hydrolytic stability of some polymers depends on the pHof the solution and others are sensitive to various components normallyfound in aqueous coatings.

Typically, a small amount (about 0.1-5.0 wt %) of water-soluble polymeris added to latex paint to achieve the following performancecharacteristics during manufacturing, storage, and applications: a) easeof formulation, b) prevention of settling of the suspended particles(latex, pigment, etc.) during storage, c) good film build duringapplications to achieve efficient hiding without excessive brush orroller drag, d) good roller spatter resistance, e) no excessive saggingafter application on a vertical surface, and f) good flow and levelingfor the formation of a smooth and continuous film with good appearance.

The above mentioned natural and synthetic thickeners provide differentdegrees of thickening efficiency and application properties. However,they invariably fail to provide all of the key performance properties ingloss paints. These key properties include good film build, flow andleveling, and gloss which are generally offered by solvent-based alkydpaints. Another drawback of these thickeners is that they may have poorcompatibility with the various paint ingredients.

To eliminate the performance deficiencies of the conventionalthickeners, a new class of thickeners, commonly referred to as“associative thickeners”, has been developed and commercialized (See E.J. Schaller and P. R. Sperry, in “Handbook of Coatings Additives”, Ed.L. J. Calbo, Vol. 2, p: 105, 1992; Marcel Dekker, Inc., New York). Thesethickeners include hydrophobically-modified water-soluble polymers. Theyundergo intermolecular association in aqueous solution and therebyexhibit enhanced solution viscosity. They can also adsorb onto thedispersed-phase particles of an aqueous dispersion and thereby form athree-dimensional network. Since they provide improved paint propertiesnot offered by conventional thickeners, they have gained commercialimportance.

Commercial nonionic synthetic thickeners exhibit often poor and variablecompatibility in paints, as exemplified by syneresis, poor coloracceptance, variable paint viscosity over time, and inadequate hidingpower.

It has been found that novel polymers and compositions according to thepresent disclosure can provide, among many other performance attributes,the important benefits of improved rheological properties. The polymersand compositions thereof may advantageously be used in variousindustrial applications including coatings. Non-limiting examples ofcoating applications include improved hide of the coating compositionson substrates.

DETAILED DESCRIPTION

Before explaining at least one embodiment of the present disclosure indetail, it is to be understood that the present disclosure is notlimited in its application to the details of construction and thearrangement of the components or steps or methodologies set forth in thefollowing description or illustrated in the drawings. The presentdisclosure is capable of other embodiments or of being practiced orcarried out in various ways. Also, it is to be understood that thephraseology and terminology employed herein is for the purpose ofdescription and should not be regarded as limiting.

Unless otherwise defined herein, technical terms used in connection withthe present disclosure shall have the meanings that are commonlyunderstood by those of ordinary skill in the art. Further, unlessotherwise required by context, singular terms shall include pluralitiesand plural terms shall include the singular.

All patents, published patent applications, and non-patent publicationsmentioned in the specification are indicative of the level of skill ofthose skilled in the art to which the present disclosure pertains. Allpatents, published patent applications, and non-patent publicationsreferenced in any portion of this application are herein expresslyincorporated by reference in their entirety to the same extent as ifeach individual patent or publication was specifically and individuallyindicated to be incorporated by reference.

All of the articles and/or methods disclosed herein can be made andexecuted without undue experimentation in light of the presentdisclosure. While the articles and methods of the present disclosurehave been described in terms of preferred embodiments, it will beapparent to those of ordinary skill in the art that variations may beapplied to the articles and/or methods and in the steps or in thesequence of steps of the method(s) described herein without departingfrom the concept, spirit and scope of the present disclosure. All suchsimilar substitutes and modifications apparent to those skilled in theart are deemed to be within the spirit, scope and concept of the presentdisclosure.

As utilized in accordance with the present disclosure, the followingterms, unless otherwise indicated, shall be understood to have thefollowing meanings.

The use of the word “a” or “an” when used in conjunction with the term“comprising” may mean “one,” but it is also consistent with the meaningof “one or more,” “at least one,” and “one or more than one.” The use ofthe term “or” is used to mean “and/or” unless explicitly indicated torefer to alternatives only if the alternatives are mutually exclusive,although the disclosure supports a definition that refers to onlyalternatives and “and/or.” Throughout this application, the term “about”is used to indicate that a value includes the inherent variation oferror for the quantifying device, the method(s) being employed todetermine the value, or the variation that exists among the studysubjects. For example, but not by way of limitation, when the term“about” is utilized, the designated value may vary by plus or minustwelve percent, or eleven percent, or ten percent, or nine percent, oreight percent, or seven percent, or six percent, or five percent, orfour percent, or three percent, or two percent, or one percent. The useof the term “at least one” will be understood to include one as well asany quantity more than one, including but not limited to, 1, 2, 3, 4, 5,10, 15, 20, 30, 40, 50, 100, etc. The term “at least one” may extend upto 100 or 1000 or more depending on the term to which it is attached. Inaddition, the quantities of 100/1000 are not to be considered limitingas lower or higher limits may also produce satisfactory results. Inaddition, the use of the term “at least one of X, Y, and Z” will beunderstood to include X alone, Y alone, and Z alone, as well as anycombination of X, Y, and Z. The use of ordinal number terminology (i.e.,“first”, “second”, “third”, “fourth”, etc.) is solely for the purpose ofdifferentiating between two or more items and, unless otherwise stated,is not meant to imply any sequence or order or importance to one itemover another or any order of addition.

As used herein, the words “comprising” (and any form of comprising, suchas “comprise” and “comprises”), “having” (and any form of having, suchas “have” and “has”), “including” (and any form of including, such as“includes” and “include”) or “containing” (and any form of containing,such as “contains” and “contain”) are inclusive or open-ended and do notexclude additional, unrecited elements or method steps. The terms “orcombinations thereof” and “and/or combinations thereof” as used hereinrefer to all permutations and combinations of the listed items precedingthe term. For example, “A, B, C, or combinations thereof” is intended toinclude at least one of: A, B, C, AB, AC, BC, or ABC and, if order isimportant in a particular context, also BA, CA, CB, CBA, BCA, ACB, BAC,or CAB. Continuing with this example, expressly included arecombinations that contain repeats of one or more items or terms, such asBB, AAA, AAB, BBC, AAABCCCC, CBBAAA, CABABB, and so forth. The skilledartisan will understand that typically there is no limit on the numberof items or terms in any combination, unless otherwise apparent from thecontext.

As used herein, the term “substantially” means that the subsequentlydescribed circumstance completely occurs or that the subsequentlydescribed circumstance occurs to a great extent or degree.

For purposes of the following detailed description, other than in anyoperating examples, or where otherwise indicated, numbers that express,for example, quantities of ingredients used in the specification andclaims are to be understood as being modified in all instances by theterm “about”. The numerical parameters set forth in the specificationand attached claims are approximations that may vary depending upon thedesired properties to be obtained in carrying out the invention.

The term “alkyl” refers to a saturated linear or branched hydrocarbongroup of 1 to 50 carbons.

The term “alkylene” as used herein refers to an unsaturated, linear orbranched hydrocarbon group of 1 to 50 carbon atoms with one or morecarbon-carbon double bonds.

The term “aryl” refers to a mono- or polynuclear aromatic hydrocarbongroup including carbocyclic and heterocyclic aromatic groups.

The term “monomer” refers to a small molecule that chemically bondsduring polymerization to one or more monomers of the same or differentkind to form a polymer.

The term “polymer” refers to a large molecule comprising one or moretypes of monomer residues (repeating units) connected by covalentchemical bonds. By this definition, polymer encompasses compoundswherein the number of monomer units may range from very few, which morecommonly may be called as oligomers, to very many. Non-limiting examplesof polymers include homopolymers, and non-homopolymers such ascopolymers, terpolymers, tetrapolymers and the higher analogues.

The term “heteroatom” refers to oxygen, nitrogen, sulfur, silicon,phosphorous, or halogen. The heteroatom(s) may be present as a part ofone or more heteroatom-containing functional groups. Non-limitingexamples of heteroatom-containing functional groups include ether,hydroxyl, epoxy, carbonyl, carboxamide, carboxylic ester, carboxylicacid, imine, imide, amine, sulfonic, sulfonamide, phosphonic, and silanegroups. The heteroatom(s) may also be present as a part of a ring suchas in heteroaryl and heteroarylene groups.

The term “moiety” refers to a part or a functional group of a molecule.

The term “acetal” refers to a functional group having two hydroxyland/or oxyalkyl groups attached to the same carbon.

The term “aminal” refers to a functional group having two amino and/oraminoalkyl groups attached to the same carbon.

The term “hemiaminal” refers to a functional group having onehydroxyl/oxyalkyl group and one amino/aminoalkyl group.

As used herein, “KU” refers to Krebs unit and is a measure of themid-shear viscosity as measured by a Kreb-Stormer viscometer.

All percentages, ratio, and proportions used herein are based on aweight basis unless other specified.

The present disclosure is directed to a lactam-functionalized polymercomprising a polymer backbone and at least one lactam-containing moietyattached to the polymer backbone. The polymer backbone can be selectedfrom the group consisting of polyacetal polyether, polyhemiaminalpolyether, polyaminal polyether, and combinations thereof. The at leastone lactam-containing moiety can be attached to at least one end of thepolymer backbone or pendant on the polymer backbone. The end(s) of thelactam-containing moieties can be in bunches. The pendantlactam-containing moiety may hang down from the polymer backbone in auniform pattern, a random pattern or in bunches. The number of the atleast one lactam-containing moiety in the lactam-functionalized polymercan be varied from 1 to 500, or from 1 to 200, or from 1 to 100, or from1 to 50.

The lactam-containing moiety herein refers to a molecule containing acyclic amide. The lactam-containing moiety can be represented by ageneral formula (I):

where R is a substituted or unsubstituted hydrocarbon diradicaloptionally having at least one heteroatom and is attached to a carbon ornitrogen atom on the lactam ring, and b is from 1 to 5.

In one non-limiting embodiment, R can be selected from the groupconsisting of a substituted or unsubstituted alkylene, alkenyl, aryl,alkylaryl, arylalkylene, arylalkenyl, cyclic, cycloaliphatic andpolycyclic, optionally having at least one heteroatom. In anothernon-limiting embodiment, R can be an alkylene having 1 to 50 carbonatoms or 1 to 30 carbon atoms or 1 to 15 carbon atoms, optionally havingat least one heteroatom.

In one aspect of the present disclosure, the at least onelactam-containing moiety can have one or both of the following generalformulas:

where L is a direct bond, or a substituted or unsubstituted alkyleneoptionally having at least one heteroatom; A is hydrogen, OX_(n)H,SX_(n)H, or NR₄X_(n)H; R₁-R₄ are identical or different and are eachindependently hydrogen, linear or branched alkyl having 1 to 30 carbons,or saturated or unsaturated hydrocarbon rings having 3 to 10 carbons,optionally having at least one heteroatom; X is the lactam-containingmoiety of Formula (II) or (III); n is from 0 to 500 or from 0 to 200 orfrom 0 to 100 or from 0 to 50; and b is from 1 to 5.

The lactam-containing moiety of the present disclosure can also berepresented by a general formula (IV):

wherein R′ and R″ are identical or different and are each independentlyhydrogen or a substituted or unsubstituted hydrocarbon diradicaloptionally having at least one heteroatom, and R″ is attached to acarbon atom on the lactam ring, and b is from 1 to 5 with the provisothat R′ or R″ or both R′ and R″ are a substituted or unsubstitutedhydrocarbon diradical optionally having at least one heteroatom.

In one non-limiting embodiment, R′ and R″ are identical or different andare each independently selected from the group consisting of asubstituted or unsubstituted alkylene, alkenyl, aryl, alkylaryl,arylalkylene, arylalkenyl, cyclic, cycloaliphatic and polycyclic,optionally having at least one heteroatom. In another non-limitingembodiment, R′ and R″ are identical or different and are eachindependently an alkylene having 1 to 30 carbon atoms, optionally havingat least one heteroatom.

In another non-limiting embodiment, R′ and R″ are identical or differentand are each independently hydrogen,

wherein L is attached to the lactam ring, and is a direct bond, or asubstituted or unsubstituted alkylene optionally having at least oneheteroatom; A is hydrogen, OX_(n)H, SX_(n) H, or NR₄X_(n)H; R₁-R₄ areidentical or different and are each independently hydrogen, linear orbranched alkyl having 1 to 30 carbons, or saturated or unsaturatedhydrocarbon rings having 3 to 10 carbons, optionally having at least oneheteroatom; X is the lactam-containing moiety of Formula (IV); n is from0 to 500; and b is from 1 to 5 with the proviso that R′ or R″ or both R′and R″ are a substituted or unsubstituted hydrocarbon diradicaloptionally having at least one heteroatom.

The lactam-containing moiety can comprise a general lactam structureincluding β-lactam, γ-lactam, δ-lactam and ε-lactam. In one non-limitingembodiment, the lactam-containing moiety can comprise a lactam structureincluding β-propiolactam, γ-butyrolactam, δ-valerolactam andε-caprolactam.

The lactam-functionalized polymer described herein above can furthercomprise at least one hydrophobic moiety to form a hydrophobicallymodified lactam-functionalized polymer. The at least one hydrophobicmoiety can be attached to at least one end of the lactam-functionalizedpolymer or pendant on the lactam-functionalized polymer. The end(s) ofthe hydrophobic moieties can be in bunches. The pendant hydrophobicmoiety may hang down from the lactam-functionalized polymer in a uniformpattern, a random pattern or in bunches.

The present disclosure is also directed to a lactam-functionalized andhydrophobically modified polymer comprising a polymer backbone, and atleast one lactam-containing moiety and at least one hydrophobic moietythat are attached to the polymer backbone. The polymer backbone can beselected from the group consisting of polyacetal polyether,polyhemiaminal polyether, polyaminal polyether, and combinationsthereof. The at least one lactam-containing moiety and the at least onehydrophobic moiety can be attached to the ends of the polymer backboneor pendant on the polymer backbone. The end-attached lactam-containingmoieties and hydrophobic moieties can be in a uniform pattern, a randompattern or in bunches. The pendant lactam-containing moiety andhydrophobic moiety may hang down from the polymer backbone in a uniformpattern, a random pattern or in bunches. The number of the at least onehydrophobic moiety in the lactam-functionalized polymer can be variedfrom 1 to 500, or from 1 to 200, or from 1 to 100, or from 1 to 50.

The lactam-containing moiety is the same as those described previously.The hydrophobic moiety can be selected from the group consisting of asubstituted or unsubstituted alkyl, alkenyl, aryl, alkylaryl, arylalkyl,arylalkenyl, cyclic, cycloaliphatic, and polycyclic, optionally havingat least one heteroatom.

In one non-limiting embodiment, the hydrophobic moiety can be afunctionalized or unfunctionalized C₁-C₄₀ alkyl optionally having one ormore heteroatoms. In another non-limiting embodiment, the hydrophobicgroup is a functionalized or unfunctionalized C₄-C₃₀ alkyl optionallyhaving one or more heteroatoms. In yet another non-limiting embodiment,the hydrophobic group is a functionalized or unfunctionalized C₆-C₂₀alkyl optionally having one or more heteroatoms.

Non-limiting examples of hydrophobic groups can include n-butyl,isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl,2-ethylhexyl, tert-octyl, iso-norbornyl, n-nonyl, n-decyl, n-undecyl,n-dodecyl, tert-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl,n-hexadecyl, n-heptadecyl, n-octadecyl, and n-eicosyl, lauryl, stearyl,2-butyl-1-octyl, phenyl, cresyl, napththyl, halogenated hydrocarbons, aprimary amino, a secondary amino, a tertiary amino, a quaternary amino,and a tertiary phosphino.

The lactam-functionalized polymers according to the present disclosurecan have a weight average molecular weight ranging from about 1,000 Dato 10,000,000 Da. In one non-limiting embodiment, thelactam-functionalized polymers can have a weight average molecularweight ranging from about 5000 Da to 5,000,000 Da. In anothernon-limiting embodiment, the lactam-functionalized polymers can have aweight average molecular weight ranging from about 10,000 Da to1,000,000 Da.

The present disclosure is directed to a method for preparing alactam-functionalized polymer comprising: 1) reacting a hydroxylpolyether or hydroxyl polyetheramine with a gem-dihalide to form apolymer backbone; and 2) reacting the polymer backbone with at least onecompound comprising at least one lactam moiety to form thelactam-functionalized polymer. The at least one compound comprising theat least one lactam moiety can further comprise at least one reactivefunctional group.

In one non-limiting embodiment, the at least one compound comprising atleast one lactam moiety and at least one reactive functional group canhave a general formula (V):

where Y is Cl, Br, I, F, OH, SH, or NR₇R₈; R₅ and R₆ are identical ordifferent and are each independently hydrogen, Cl, Br, I, F, OH, SH,NR₇R₈, linear or branched alkyl having 1 to 30 carbons, or saturated orunsaturated hydrocarbon rings having 3 to 10 carbons, optionally havingat least one heteroatom; R₇ and R₈ are identical or different and areeach independently hydrogen, linear or branched alkyl having 1 to 30carbons, or saturated or unsaturated hydrocarbon rings having 3 to 10carbons, optionally having at least one heteroatom; a is from 1 to 20 orfrom 1 to 8; and b is from 1 to 5.

In another non-limiting embodiment, the at least one compound comprisingat least one lactam moiety and at least one reactive functional groupcan have a general formula (VI):

wherein W and W′ are identical or different and are each independentlyhydrogen or

where Y is Cl, Br, I, F, OH, SH, or NR₇R₈; R₅ and R₆ are identical ordifferent and are each independently hydrogen, Cl, Br, I, F, OH, SH,NR₇R₈, linear or branched alkyl having 1 to 30 carbons, or saturated orunsaturated hydrocarbon rings having 3 to 10 carbons, optionally havingat least one heteroatom; R₇ and R₈ are identical or different and areeach independently hydrogen, linear or branched alkyl having 1 to 30carbons, or saturated or unsaturated hydrocarbon rings having 3 to 10carbons, optionally having at least one heteroatom; a is from 1 to 20 orfrom 1 to 8; and b is from 1 to 5 with the proviso that W or W′ or bothW and W′ are a substituted or unsubstituted hydrocarbon diradicaloptionally having at least one heteroatom.

In yet another non-limiting embodiment, the at least one compoundcomprising at least one lactam moiety and at least one reactivefunctional group can have a general formula (VII):

where Y is O, S, or NR₇; Z is O, S, or NR₇; R₅ and R₆ are identical ordifferent and are each independently hydrogen, Cl, Br, I, F, OH, SH,NR₇R₈, linear or branched alkyl having 1 to 30 carbons, or saturated orunsaturated hydrocarbon rings having 3 to 10 carbons, optionally havingat least one heteroatom; R₇ and R₈ are identical or different and areeach independently hydrogen, linear or branched alkyl having 1 to 30carbons, or saturated or unsaturated hydrocarbon rings having 3 to 10carbons, optionally having at least one heteroatom; a is from 1 to 20 orfrom 1 to 8; and b is from 1 to 5.

In yet another non-limiting embodiment, the at least one compoundcomprising at least one lactam moiety and at least one reactivefunctional group can have a general formula (VIII):

wherein V and V′ are identical or different and are each independentlyhydrogen or

wherein Y is O, S, or NR₇; Z is O, S, or NR₇; R₅ and R₆ are identical ordifferent and are each independently hydrogen, Cl, Br, I, F, OH, SH,NR₇R₈, linear or branched alkyl having 1 to 30 carbons, or saturated orunsaturated hydrocarbon rings having 3 to 10 carbons, optionally havingat least one heteroatom; R₇ and R₈ are identical or different and areeach independently hydrogen, linear or branched alkyl having 1 to 30carbons, or saturated or unsaturated hydrocarbon rings having 3 to 10carbons, optionally having at least one heteroatom; a is from 1 to 20 orfrom 1 to 8; and b is from 1 to 5 with the proviso that V or V′ or bothV and V′ are a substituted or unsubstituted hydrocarbon diradicaloptionally having at least one heteroatom.

The method described herein above can further comprise 3) reacting thelactam-functionalized polymer with at least one compound comprising atleast one hydrophobic moiety.

In one aspect, a method for preparing the lactam-functionalized polymerscan comprise: 1) reacting a hydroxyl polyether or hydroxylpolyetheramine with a gem-dihalide to form a polymer backbone; 2)reacting the polymer backbone with at least one compound comprising atleast one hydrophobic moiety to form a hydrophobically modified polymer;and 3) reacting the hydrophobically modified polymer with at least onecompound comprising at least one lactam moiety. The at least onecompound comprising the at least one lactam moiety can further compriseat least one reactive functional group.

In another aspect, a method for preparing the lactam-functionalizedpolymers can comprise: 1) reacting a hydroxyl polyether or hydroxylpolyetheramine with a gem-dihalide to form a polymer backbone; and 2)reacting the polymer backbone with at least one compound comprising atleast one hydrophobic moiety and at least one compound comprising atleast one lactam moiety. The at least one compound comprising the atleast one lactam moiety can further comprise at least one reactivefunctional group.

The at least one compound comprising the at least one lactam moiety canfurther comprise at least one reactive functional group is the same asthose described previously.

In one non-limiting embodiment, the compound comprising at least onelactam moiety and at least one reactive functional group can be selectedfrom the group consisting of 1-chloro-2-pyrrolidinone,1-bromo-2-pyrrolidinone, 1-amino-2-pyrrolidinone,1-hydroxy-2-pyrrolidinone, 1-(hydroxymethyl)-2-pyrrolidinone,2-oxo-1-pyrrolidinecarboxaldehyde, 1-(chloromethyl)-2-pyrrolidinone,1-(bromomethyl)-2-pyrrolidinone, 1-(aminomethyl)-2-pyrrolidinone,1-(2-aminoethyl)-2-pyrrolidinone, 1-(2-hydroxyethyl)-2-pyrrolidinone,1-(2-chloroethyl)-2-pyrrolidinone, 1-(2-bromoethyl)-2-pyrrolidinone,1-(3-aminopropyl)-2-pyrrolidinone, 1-(3-hydroxypropyl)-2-pyrrolidinone,1-(3-chloropropyl)-2-pyrrolidinone, 1-(3-bromopropyl)-2-pyrrolidinone,1-(3-fluoropropyl)-2-pyrrolidinone, 1-(2-propyn-1-yl)-2-pyrrolidinone,2-oxo-1-pyrrolidineacetic acid, 1-ethenyl-2-pyrrolidinone,2-oxo-1-pyrrolidinonecabonitrile, 1-(2-propn-1-yl)-2-pyrrolidinone, andcombinations thereof. Further useful examples of compounds comprising atleast one lactam moiety may be found in U.S. Pat. Nos. 2,775,599;3,136,766; 4,801,400; 4,842,858; 5,352,251; 5,458,660; 5,507,843; and6,261,327, each publication of which is herein incorporated in itsentirety by reference.

In another non-limiting embodiment, the compound comprising at least onelactam moiety and at least one reactive functional group can be acompound comprising at least one lactam moiety and at least on cyclicether moiety. Non-limiting examples of the compounds comprising at leastone lactam moiety and at least one cyclic ether moiety can include, butare not limited to N-(2,3-epoxypropyl)pyrrolidinone,N-(3,4-epoxybutyl)pyrrolidinone, N-(4,5-epoxypentyl)pyrrolidinone,N-ethylpyrrolidone glycidyl ether, and the like.

The compounds comprising at least one hydrophobic moiety can berepresented by the following general chemical formula:

Y-R-X

wherein R is a hydrocarbon, and X is a hydrogen or a reactive functionalgroup selected from the group consisting of hydroxyl, halogen, epoxide,glycidyl ether, amino, sulfhydryl, and combinations thereof. Y is areactive functional group selected from the group consisting ofhydroxyl, halogen, epoxide, glycidyl ether, amino, sulfhydryl, andcombinations thereof. The hydrocarbon can be selected from the groupconsisting of a substituted or unsubstituted alkyl, alkenyl, aryl,alkylaryl, arylalkyl, arylalkenyl, cyclic, cycloaliphatic, andpolycyclic, optionally having at least one heteroatom.

In one non-limiting embodiment, the compound comprising at least onehydrophobic moiety can be selected from the group consisting of glycidylethers such as ethyl glycidyl ether, butyl glycidyl ether, pentylglycidyl ether, hexyl glycidyl ether, heptyl glycidyl ether, octylglycidyl ether, 2-ethylhexyl glycidyl ether, norbornyl glycidyl ether,nonyl glycidyl ether, decyl glycidyl ether, undecyl glycidyl ether,dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidylether, pendecyl glycidyl ether, hexadecyl glycidyl ether, heptadecylglycidyl ether, octadecyl glycidyl ether, eicoyl glycidyl ether, laurylglycidyl ether, stearyl glycidyl ether, 2-butyl-1-octyl glycidyl ether,phenyl glycidyl ether, naphthyl glycidyl ether, cresyl glycidyl ether;halogenated hydrocarbons such as 1-bromobutane, 1-bromopentane,1-bromohexane, 1-bromoheptane, 1-bromooctane, 1-bromononane,1-bromodecane, 1-bromoundecane, 1-bromododecane, 1-bromotridecane,1-bromotetradecane, 1-bromopentadecane, 1-bromohexadecane,1-1-bromoheptadecane, 1-bromooctadecane, primary amines, secondaryamines, tertiary amines, quaternary amines, tertiary phosphines andcombinations thereof.

Non-limiting examples of compounds comprising at least one hydrophobicmoiety can include ethoxylated nonylphenols such as IGEPAL® CO 890;ethoxylated tallow amines such as Rhodameen® series of compounds; andethoxylated fatty tertiary amines such as Rhodameen® T-50 and Rhodameen®T-12/90, which are all commercially available from Solvay. More examplescan include, but are not limited to, bisphenol-A polyethoxylatesavailable from PPG Industries; DL-3-octadecyloxy-1,2-propanediol;1-phenyl-1,2-ethane diol; 1H, 1H, 2H,3H,3H-pentafluoroundecane-1,2-diol; 1,3-dioxane-5,5-dimethanol;3-fluorobenzal bromide; (dichloromethyl)dimethyl-n-propylsilane;1-hexadecylamine; 4-fluorobenzene boronic acid; and the like.

The hydroxyl polyether or hydroxyl polyetheramine comprises at least onehydroxyl group. The hydroxyl polyetheramine comprises at least one aminogroup.

The hydroxyl polyether can be dihydroxyl polyether. In one non-limitingembodiment, the dihydroxyl polyether can be a polyalkylene glycolbearing terminal hydroxyl groups. In another non-limiting embodiment,the dihydroxyl polyether can be a polyethylene glycol (PEG).Non-limiting examples of the PEGs may be found in the ACS Symposium Booktitled ‘Poly(ethylene glycol) Chemistry and Biological Applications’,Editors: J. Milton Harris and Samuel Zalipsky, Volume 680, 1997, thepublication of which is herein incorporated in its entirety byreference. PEGs, ranging in weight average molecular weight from about100 to about 20,000 Daltons, can be obtained from several commercialsources. For example, various grades of low weight average molecularweight polyethylene glycols (molecular weight range of 4,000-8000Daltons) are commercially available from The Dow Chemical Company underthe trademark of Carbowax. In yet another non-limiting embodiment, thealpha, omega-dihydroxy polyether is a poly(ethylene oxide) polymer.Various grades of poly(ethylene oxide) polymers are commerciallyavailable from The Dow Chemical Company under the trademark of Polyox.

In one non-limiting embodiment, the polyetheramine can be represented bythe following general chemical formula:

wherein x is an integer ranging from 2 to 100 and each A isindependently selected from the C₂-C₈ alkylene moieties. Non-limitingexamples of polyetheramines can include Jeffamine® diamines of the E,ED, and EDR series that are commercially available from the HuntsmanCorp.

Generally, any gem-dihalide may be used in the process for preparing thepolyacetal polyether, polyhemiaminal polyether or polyaminal polyether.Non-limiting examples of gem-dihalides can include dibromomethane,dichloromethane, 1,1-dichlorotoluene (C₆H₅CHCl₂), 1,1-dichloroethane(CH₃CHCl₂), and 1,1-dibromoethane (CH₃CHBr₂).

In one non-limiting embodiment, a lactam-functionalized polyacetalpolyether (PAPE) can be prepared as follows. An alkalized PAPE isproduced by reacting a dihydroxyl polyether, such as a polyethyleneglycol (PEG), with a gem-dihalide, such as dibromomethane. The alkalizedPAPE is then reacted with a compound comprising at least one lactammoiety and at least one cyclic ether moiety, such asN-[2-(2-oxiranylmethoxy)ethyl]-2-pyrrolidone (EPGE). Scheme 1 shows theschematic diagram for the preparation of the lactam-functionalized PAPE(EPGE PAPE).

where r₁ and r₁′=1 to 500, r₂ and r₂′=1-500, r₃ and r₃′=1 to 500, r₄=0to 500, and r₅=0 to 500, with the proviso that at least one of r₄ and r₅is non-zero.

The EPGE PAPE shown as above results from the predominant additionreaction at the less hindered face of the epoxide moiety on EPGE,resulting in one or more lactam-functional alkylene moieties A on thepolymer backbone as shown in Scheme 2. The epoxide ring opening can alsooccur by addition reaction at the more hindered face of the epoxidemoiety. In such a case, the resulting polymer backbone may comprise oneor more lactam-functional alkylene moieties B as shown in Scheme 2.

In general, the description of reactions across two faces of an epoxidemoiety may be extended to the reaction of any compound comprising atleast one epoxide moiety, such as the epoxy-containing compounds listedin this specification, and any nucleophile, such as polyacetalpolyethers.

A solvent can be used for the synthesis of the polymers according to thepresent disclosure. Any solvent without active hydrogens may be used. Inone non-limiting embodiment, oxygenated hydrocarbon solvents bearing 2to 30 carbons can be used. Non-limiting examples of solvents can includetoluene, xylene, aliphatic hydrocarbons, dialkyl ethers of alkyleneglycols and diethoxymethane.

Any strong base capable of reacting with the terminal active hydrogensof the polyacetal polyether, polyhemiaminal polyether orpolyaminal-polyether to form the corresponding dianion, can be used inthe process of making the lactam-functionalized polymer. Non-limitingexamples of bases can include alkali metal hydrides, alkali metalhydroxides, alkali metal carbonates, and organic bases.

The present disclosure relates to a method of thickening a compositioncomprising adding the lactam-functionalized polymer describedhereinabove into the composition. Examples of the compositions caninclude, but are not limited to, coating compositions, constructioncompositions, personal care compositions, oilfield compositions,drilling fluids, drilling muds, cementing fluids, servicing fluids,gravel packing muds, fracturing fluids, completion fluids, workoverfluids, spacer fluids, household, industrial and institutionalcompositions, pharmaceutical compositions, food compositions, biocides,adhesives, inks, papers, polishes, membranes, metal working fluids,plastics, textiles, printing compositions, lubricants, preservatives,agrochemicals, and wood-care compositions.

The present disclosure also relates to a coating composition comprisingthe lactam-functionalized polymers as described hereinabove. The coatingcomposition may further comprise at least one additive selected from thegroup consisting of solvents/cosolvents, secondary rheology modifiers,thixotropic agents, binders, crosslinkers, pH adjustment agents,pigments/fillers, flow-control agents, gloss-control agents, coalescentagents, flexibilizing resins, surfactants, waxes, wetting agents,dispersing agents, plasticizers, anti-oxidants, UV radiation absorbers,biocides, extenders, colorants, adhesion promoters, defoamingagents/defoamers, driers, matting agents, and combinations thereof.

Examples of the pigments/fillers can include, but are not limited to,calcium carbonate, mica, barium sulphate, lithopones, zinc oxide, zincsulphide, titanium dioxide (anatase, rutile), chalk, precipitatedcalcium carbonate, calcite, dolomites, silicon dioxide, silicic acids,silica flour, pyrogenic silicic acids, precipitated silicic acids,silicates, talc, kaolin, barium sulfates, magnesium silicates, lead,lead oxides, barytes, blanc fixe, sand and glass beads. Specialpigments/fillers can include graphene, graphite, carbon nanotubes,carbon, copper, silver, nanosilver, titanium nanotubes, speciallydecorated inorganic particles and structures, and the like.

Non-limiting examples of the solvents/cosolvents can include aromatichydrocarbon solvents such as benzene, toluene and xylene, ethyl benzene,isopropyl benzene, alcohols (ethylene glycol monobutyl ether, ethyleneglycol monomethyl ether, diethylene glycol mono butyl ether, diethyleneglycol monomethyl ether, diethylene glycol monoethyl ether, hexanol,octanol, ethanol, isopropanol, butanol, n-butanol, ethylene glycol,diethylene glycol, ketones (acetone, methyl ethyl ketone, methylisobutyl ketone, cyclohexanone), diacetone alcohol, dimethyl formamide,n-methyl-2-pyrrolidone, butyrolactone, ethyl acetate, butyl propionate,water, and the like.

Non-limiting examples of the binders can include latex emulsionpolymers, which are the polymerization products of one or moreethylenically unsaturated monomers. Examples of ethylenicallyunsaturated monomers can include, but are not limited to, acrylic acid,acrylonitrile, acetoacetoxy ethyl methacrylate, acetoacetoxy ethylacrylate, butyl acrylate, butadiene, butyl methacrylate, butylacrylamide, chloromethyl styrene, crotonic acid, ethyl acrylate, ethylacrylamide, ethylene, ethyl methacrylate, ethylhexyl acrylate,2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, glycidyl methacrylate,hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, isobutylacrylate, isobutyl methacrylate, isoprene, iso-octyl acrylate, iso-octylmethacrylate itaconic acid, methyl acrylate, octyl acrylate, octylmethacrylate, methyl methacrylate, methacrylic acid, α-methyl styrene,styrene, vinyl chloride vinyl naphthalene, vinyl toluene, vinylidenechloride, vinyl acetate, and the like.

Other binders used in the present disclosure can include, but are notlimited to alkyd resins, polyurethane resins, epoxy resins, and thelike. Alkyd resins are generally comprised of polybasic acids,polyhydric alcohols, and fatty acids which may be unsaturated. Thepolybasic acids such as aromatic, aliphatic and alicyclic saturated andunsaturated compounds, such as adipic acid, chlorendic acid,heptanedioic acid, isophthalic acid, maleic acid, napthalic acid,phthalic acid, sebacic acid, succinic acid, trimellitic acid,terephthalic acid, and tetrahydrophthalic acid. Polyhydric alcoholcomponents include 1,3-butylene glycol, diethylene glycol,dipentaerythritol, dipropylene glycol, ethylene glycol, glycerin,1,6-hexanediol, neopentyl glycol, pentaerythritol, propylene glycol,sorbitol, trimethylol ethane, trimethylol propane and triethyleneglycol. Fatty acids used in the manufacture of alkyds commonly includedehydrated castor oil, coconut oil, cottonseed oil, fish oil, linseedoil, oiticica oil, tung oil, safflower oil, soya oil, tall oil acids,and the like.

Polyurethane resins are formed from polyisocyanate (aliphatic, aromatic,or combinations thereof) compounds. Examples of aliphatic isocyanatesinclude butane diisocyanate, 4,4′-diisocyanatodicyclohexylmethane,hexamethylene diisocyanate, hexahydroxylylene diisocyanate, isophoronediisocyanate, 1-methyl-2,4(2,6)-diisocyanato cyclohexane, norbornanediisocyanate, and tetramethylxylylene diisocyanate. Examples ofaliphatic and aromatic isocyanates include 4,4′-biphenylenediisocyanate, 4-chloro-1,3-phenylene diisocyanate, 1,4-cyclohexylenediisocyanate, 1,10-deca-ethylene diisocyanate, methylene bis-(4-phenylisocyanate), 4,4-methylene-bis(cyclohexyl isocyanate), 1,5-naphthalenediisocyanate, 1,3-phenylene diisocyanate, 2,4-tolylene diisocyanate,2,6-tolylene diisocyanate, 1,4-tetramethylene diisocyanate,1,5-tetrahydronaphthalene diisocyanate, and the like.

In addition to isocyanates, alcohols and carboxylic acids, which formpolyester compositions, can also be used in the preparation ofpolyurethane resins. The polycarboxylic acids may be of an aliphatic,cycloaliphatic, aromatic and/or heterocyclic nature and may comprisehalogen atoms and/or unsaturated moieties. Suitable acids include adipicacid, azeleic acid, bis-glycol terephthalate, dimeric fatty acids,dimethyl terephthalate, endomethylenetetrahydrophthalic anhydride,fumaric acid, glutaric anhydride, hexahydrophthalic anhydride,isophthalic acid, maleic acid, maleic anhydride, phthalic anhydride,phthalic acid, suberic acid, succinic acid, sebacic acid,tetrahydrophthalic anhydride and tetrachlorophthalic anhydride.Polyhydric alcohols examples include 1,4-, 1,3- and 2,3-butylene glycol,cyclohexanedimethanol (1,4-bis-hydroxymethylcyclohexane), diethyleneglycol, dipropylene glycol, dibutylene glycol, ethylene glycol, 1,2- and1,3-propylene glycol, 1,6-hexanediol, 2-methyl-1,3-propanediol,neopentylglycol, 1,8-octanediol, polyethylene glycol, polypropyleneglycol, polybutylene glycol, triethylene glycol and tetraethyleneglycol. Polyesters comprising carboxyl groups and terminal carboxylgroups are envisioned. Diols comprising carboxyl or carboxylate groupswhich are suitable to support ionic or potentially ionic groups areenvisioned. Such moieties can be constructed by dihydroxysuccinic acid,dimethylolacetic acid, 2,2-dimethylolpropionic acid,2,2-dimethylolbutyric acid and 2,2-dimethylolpentanoic acid. Polyestersconstructed from lactones are also envisioned. Polycarbonates comprisinghydroxyl groups are useful and are prepared by reacting diols withdicarbonates such as diphenyl carbonate or phosgene. Polyetherscomprising diols, formed from polymers derived from ethylene oxide,propylene oxide and/or tetrahydrofuran are also useful. An aminefunctionality can be employed to introduce terminal hydroxylfunctionality, with compounds such as diethanolamine, ethanolamine,N-methylethanolamine, propanolamine,N,N,N′-tris-2-hydroxyethyl-ethylendiamine.

Epoxy resins are comprised primarily of linear chain molecules. Thesemolecules are formed from the reaction of bisphenols with halohydrins toyield epoxy resins containing epoxy groups. Common bisphenols includebisphenol-A, bisphenol-F, bisphenol-S, and 4,4′ dihydroxy bisphenol.Common halohydrins include epichlorohydrin, dichlorohydrin, and1,2-dichloro-3-hydroxypropane. Examples of commercially available epoxyresins include D.E.R.™ 333 and D.E.R.™ 661 from The Dow ChemicalCompany; EPON™ 828, EPON™ 836, and EPON™ 1001 from Momentive SpecialtyChemicals Inc.; Ciba-Geigy epoxy resins GT-7013, GT-7014, GT-7074,GT-259 from Huntsman; and Ancarez™ AR 555 from Air Products.

Non-limiting examples of the secondary rheology modifiers can includecelluloses and cellulose derivatives, guars and guar derivatives,modified ureas, polyurethane thickeners and associative thickeners,alkali swellable emulsions (ASEs), hydrophobically modified alkaliswellable emulsions (HASEs), hydrophobically modified polyurethanes(HEURs), hydrophobically modified polyethers (HMPEs), attapulgites,hydrophobically modified polyacetal polyethers (HMPAPEs), acrylatethickeners, amides and organic derivatives, fumed silicas, syntheticlayered silicates, organoclays, mixed minerals, thixotropy boosters,polyalkylene ether derivatives, starches, polyacrylates, and the like.

Non-limiting examples of the pH adjustment agents can includemonoethanol amine, triethanol amine, methylaminoethanol,2-amino-2-methyl-1-propanol, 2-(n-butylamino) ethanol, ammoniumhydroxide, ammonia, caustic, potassium hydroxide, formic acid, aceticacid, citric acid, organic acids, minerals acids, hydrochloric acid,sulfuric acid, nitric acid, phosphoric acid, and the like.

Non-limiting examples of biocidal agents can include2-n-octyl-3-isothiazolone, chlorothalonil, carbendazim, diuron,isothiazolone, 2-octyl-2H-isothiazol-3-one (OIT), iodopropynyl butylcarbamate (IPBC), sodium 2-pyridinethiol-1-oxide, zinc2-pyridinethiol-1-oxide, 1,2-dibromo-2,4-dicyanobutane,2-(4-thiazolyl)-benzimidazole, thiabendazole, tebuconazole, methylenebis(thiocyanate), 2-(thiocyano-methylthio)-benzothiazole, octhilinone,barium metaborate, propiconazole, diiodomethyl p-tolyl sulfone,3-iodo-2-propynyl butyl carbamate, n-(trichloromethylthio) phthalimide,tributyltin benzoate, alkyl amine hydrochlorides,n-trichloromethylthio-4-cyclohexene-1,2-dicarboximide,2-methylthio-4-tert-butyl-amino-6-cyclopropylamino-s-triazine,tetrachloroisophthalonitrile, zinc dimethyldithiocarbamate, zinc2-mercaptobenzothiazole, trans-1,2-bis(n-propyl-sulfonyl ethane,4,5-dichloro-2-n-octyl-3-(2H)-isothiazolone,4,5-dichloro-2-octyl-4-isothiazolin-3-one (DCOIT), carbendazim, Irgarol,10,10′-oxybisphenoxarsine, triclosan,2-methylthio-4-tert-butyl-amino-6-cyclopropylamino-s-triazine,n-cyclopropyl-N′-(1,1-dimethylethyl)-6-)methylthio)-1,3,5-triazine-2,4-diamine,zinc dimethyldithiocarbamate (Ziram), Irgarol® 1051 (commerciallyavailable from BASF SE), tributyltin oxide (TBTO),5-chloro-methyl-2H-isothiazol-3-one/2-methyl-2H-isothiazol-3-one(CIT/MIT), benzisothiazolinone (BIT), methylisothiazolinone (MIT),hexahydro-1,3,5-tris(2-hydroxyethyl)-S-triazine, sodium pyrithione, zinc2-pyridinethiol-1-oxide, 1,2-benzoisothiazolin-3-one, glutaraldehyde,2,2-dibromo-3-nitrilopropionamide (DBNPA), poly(hexamethylenebiguanide)hydrochloride (PHMB), 2-bromo-2-nitropropane-1,3-diol (Bronopol),1,2-dibromo-2-4-dicyanobutane,1-bromo-1-(bromomethyl)-1,3-propanedicarbonitrile,2,2-dibromo-3-nitrio-propionamide, benzyl bromoacetate,1-bromo-1-(bromomethyl)-1,3-propanedicarbonitrile, Dazomet,dodecylguanidine hydrochloride, methylene dithiocyanate,1-methyl-3,5,7-triaza-1-azoniaadamantane chloride,2-bromo-4′-hydroxyacetophenone, dibromo-3-nitrilopropionamide,1,2-benzisothiazolin-3-one, hexahydrotriazine, bromo-beta-nitrostyrene,ethyldihydro-1H,3H,5H-oxazolo(3,4-C)oxazole,acetoxy-2,4-dimethyl-m-dioxane, nitrobutyl morpholine,ethyl-2-nitrotrimethylene dimorpholine, sodium o-phenylphenate,chloroallyl-3,5,7-azoniaadamantane chloride, sodium salt of biphenylol,tributyltin benzoate, alkylamine hydrochlorides, mixture of monocyclicoxazolidines,n-methyl-2-hydroxymethyleneoxypropyl-2′-hydroxypropylamine, sodiumhydroxymethyl glycinate, mixture of bicyclic oxazolidines,1,3-bis(hydroxymethyl)-5,5-dimethyl hydantoin, hydroxymethyl5,5-dimethylhydantoin, 5-chloro-2-methyl-4-isothiazolin-3-one,2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, andcombinations.

Non-limiting examples of colorants can include pigments and/or dyes.Suitable pigment materials can be found in Hunger's “Industrial OrganicPigments,” Itoh's “Dictionary of Pigments,” and Leach and Pierce's“Printing Ink Manual.” Examples of inorganic pigments can include, butare not limited to, pigment blacks (lamp, furnace, channel blacks), ironoxides (red, yellow, brown, black, transparent, etc.), spinel black,chromium oxides green, chromate yellows, iron blues, zinc chromate,molybdate orange, molybdate reds, ultramarine, cadmium, mixed phasepigments (nickel titanium yellow, chromium titanium yellow, cobaltgreen, cobalt blue, zinc iron brown, iron manganese black), all types ofmetallic powder pigments such as aluminum powder, gold powder, silverpowder, copper powder, bronze powder, and brass powder; or their metalflake pigments; mica flake pigment; mica flake pigments which have beencoated with metallic oxides; mica shape oxide pigments, and the like.

Organic pigments can include, but are not limited to, monoazo pigments(acetoacetarylide, benzimidazolone, naphthol AS, pigmented b-naphtholdyes), disazo pigments (azo condensation pigments, dipyrazolone),polycyclic pigments (quinacridone, dioxazine, perylene,diketopyrrolo-pyrrole, isoindoline), and metal complex pigments(Cu-phthalocyanines). Examples of the dyes can include metal complexdyes, anionic dyes, azo dyes, and the like.

Cellulose derivatives can include, but are not limited to, ethylcellulose (EC), hydroxyethyl cellulose (HEC), hydroxypropyl cellulose(HPC), ethylhydroxyethyl cellulose (EHEC), carboxymethyl cellulose(CMC), carboxymethylhydroxyethyl cellulose (CMHEC),hydroxypropylhydroxyethyl cellulose (HMHEC), methyl cellulose (MC),methylhydroxypropyl cellulose (MHPC), methylhydroxyethyl cellulose(MHEC), carboxymethylmethyl cellulose (CMMC), hydrophobically modifiedcarboxymethyl cellulose (HMCMC), hydrophobically modified hydroxyethylcellulose (HMHEC), hydrophobically modified hydroxylpropyl cellulose(HMHPC), hydrophobically modified ethylhydroxyethyl cellulose (HMEHEC),hydrophobically modified carboxymethylhydroxyethyl cellulose (HMCMHEC),hydrophobically modified hydroxypropylhydroxyethyl cellulose (HMHPHEC),hydrophobically modified methyl cellulose (HMMC), hydrophobicallymodified methylhydroxypropyl cellulose (HMMHPC), hydrophobicallymodified methylhydroxyethyl cellulose (HMMHEC), hydrophobically modifiedcarboxymethylmothyl cellulose (HMCMMC), cationic hydroxyethyl cellulose(cationic HEC), cationic hydrophobically modified hydroxyethyl cellulose(cationic HMHEC), nano fibrillated cellulosics (NFC), andmicrofibrillated cellulosics (MFC).

Guar derivatives can include, but are not limited to, carboxymethylguar, carboxymethylhydroxypropyl guar, cationic hydroxypropyl guar,hydroxyalkyl guar such as hydroxyethyl guar, hydroxypropyl guar, andhydroxybutyl guar, carboxylalkyl guars such as carboxymethyl guar,carboxylpropyl guar, carboxybutyl guar, and the like.

Examples of the defoaming agents or defoamers can include, but are notlimited to, silicone defoamers, silicone defoamers comprisingpolysiloxane and hydrophobic particles, silicone-free defoamerscomprising hydrophobic particles and polymers, silicone-free defoamerscomprising polymers, mineral oil defoamers comprised of paraffin basedmineral oil, hydrophobic particles, and polysiloxanes.

Surfactants can provide excellent surface tension reducing capabilitiesfor substrate wetting. Surfactants used in the present disclosure can benonionic and anionic surfactants.

Examples of the nonionic surfactants can include, but are not limitedto, C₁₂-C₁₈ fatty alcohol ethoxylates, C₁₂-C₁₄ fatty alcoholethoxylates, C₁₆-C₁₈ fatty alcohol ethoxylates, C₁₃-C₁₅ oxo alcoholethoxylates, C₁₀-C₁₈ alcohol ethoxylates, C₁₃ oxo alcohol ethoxylates,C₁₀ Guerbet alcohol ethoxylates, C₁₀ Guerbet alcohol alkoxylates, C₁₀oxo alcohol ethoxylates, alkyl polyglucosides (e.g., C₈-C₁₀ alkylpolyglucoside, C₈-C₁₄ alkyl polyglucoside, C₁₂-C₁₄ alkyl polyglucoside,blends of C₁₂-C₁₀ alkyl polyglucoside on inorganic and organic carrier,amine ethoxylates (e.g., oleyl amine+12 EO, coco amine+˜12 EO),aminopolyol (e.g., triethanol amine+18 EO, ethylene diamine+4 PO), alkylpyrrolidones (e.g., N-octyl pyrrolidone, N-butyl pyrrolidone, N-dodecylpyrrolidone), resin precursors and additives (e.g., Bisphenol Aethoxylates, BIS A+3 EO, BIS A+4 EO, BIS A+6 EO), emulsifiers andsolubilizers (e.g., 4-C₁₀₋₁₃-sec-alkyl derivatives of benzenesulfonicacid calcium salts, castor oil+˜20 EO, castor oil+˜35 EO, castor oil+˜40EO, epoxidized vegetable oil, ethoxylated rape seed oil, sorbitanesterethoxylated, decyl alcohol+˜3 EO, C₈ fatty alcohol+4 EO, fatty alcoholethoxylate, C₈-C₁₀ fatty alcohol+˜5 EO, C₁₂-C₁₄ fatty alcohol+˜50 EO,ethoxylated sorbitan trioleate, castor oil ethoxylate, phenolethoxylate, alcohol ethoxylate, ethoxylated mono-/di glyceride), foamsuppressors (e.g., polyalkoxyester and solvent, fatty alcoholalkoxylate, carboxylic acid ester, phosphoric acid ester, combination ofparaffin and silicon on carrier, alkyl polyalkylene glycol ether,Guerbet alcohol C₁₆+˜2 EO, fatty alcohol alkoxylate), low-foamingnonionic surfactants (e.g., fatty alcohol alkoxylate, modified fattyalcohol polyglycol ether, amine alkoxylate, end-capped Guerbet alcoholalkoxylate, end-capped fatty alcohol alkoxylate, PO/EO blockcopolymers), lauramine oxide, cocamidopropylamine oxide, alkylamidopropyl betaine, polyglycol ether of an aliphatic diol, oleic acidamide+10 EO, emulsifiable methyl canolate, unsaturated fatty alcoholethoxylate, fatty alcohol poly glycol ethers, fatty alcohol poly glycolethers with fatty acid, unsaturated fatty alcohol ethoxylate),polyethylene glycols, polypropylene glycols, methyl polyethyleneglycols, alkyl polyalkylene glycol copolymers, alkyl polypropyleneglycols, polyfunctional polyalkylene glycols, reactive polyalkyleneglycols.

Other nonionic surfactants can include, but are not limited to,alkylphenol ethoxylates such as nonylphenol ethoxylates and octylphenolethoxylates, secondary alcohol alkoxylates such as secondary alcoholethoxylates (TERGITOL™15-S-9, commercially available from The DowChemistry Company), and primary alcohol alkoxylates.

Examples of anionic surfactants can include, but are not limited to,sodium salt of lauryl ether sulfate+2 EO, sodium salt of iso-tridecylalcohol ether sulfate+20 EO, sodium salt of fatty alcohol ethersulfate+2 EO, sodium salt of fatty alcohol ether sulfate+4 EO, sodiumsalt of fatty alcohol ether sulfate+7 EO, sodium salt of fatty alcoholether sulfate+12 EO, sodium salt of fatty alcohol ether sulfate+30 EO,sodium salt of fatty alcohol ether sulfate+50 EO, sodium salt of C₁₂-C₁₄fatty alcohol ether sulfate+1 EO, sodium salt of C₁₂-C₁₄ fatty alcoholether sulfate+2 EO, sodium salt of C₁₂-C₁₄ fatty alcohol ether sulfate+3EO, ammonium salt of C₈-C₁₄ fatty alcohol sulfate, sodium salt of2-ethylhexyl sulfate, sodium salt of C₁₆-C₁₈ fatty alcohol sulfate,sodium salt of C₁₂ fatty alcohol sulfate, sodium salt of C₁₂-C₁₄ fattyalcohol sulfate, sodium salt of C₁₂-C₁₆ fatty alcohol sulfate, sodiumsalt of C₁₂-C₁₈ fatty alcohol sulfate, sodium salt of C₁₆-C₁₈ fattyalcohol sulfate, sodium salt of C₈ fatty alcohol sulfate, sodium salt oflinear C₁₀-C₁₃ alkyl benzene sulfonate, sodium salt of linear C₁₀-C₁₃alkyl benzene sulfonic acid, potassium salt of oleic acid sulfonate.

Other surfactants used in the present disclosure can include, but arenot limited to, ester quats, sodium salt of alkyl ether phosphate,sodium-N-lauryl-β-iminodipropionate, acid phosphoric ester of a fattyalcohol ethoxylate+3 EO, sodium salt of mono-alkenyl sulfosuccinamate,sodium salt of mono-alkenyl sulfosuccinate+5 EO, sodium salt ofdi-isodecyl sulfosuccinate, sodium dioctylsulphosuccinate, acidphosphoric ester, amine salt of dodecylbenzenesulphonate, alkyl esterphosphate, and the like.

Non-limiting examples of coalescent agents can include ethylene glycolmonobutyl ether acetates, diethylene glycol monoethyl ether, lowermonoalkyl ethers of ethylene or propylene glycol (propylene glycolmethyl ether), dimethyl succinate, diethyl succinate, diisopropylsuccinate, toluates (e.g., 2-ethoxyethyl p-toluate, 2-propoxyethylo-toluate, 2-ethoxyethyl o-toluate, 2-ethoxyethyl benzoate,2-(2-ethoxyethoxy)ethyl p-toluate), benzoates (e.g.,2-(2-ethoxyethoxy)ethyl benzoate, 2-propoxyethyl benzoate,2-methoxy-1-methylethyl benzoate,2-(2-methoxy-1-methylethoxy)-1-methylethyl benzoate,2-propoxy-1-methylethyl benzoate). Levulinic acid ester of2-hexyl-1-decanol, levulinic acid ester of1-tetradecanol/2-hexyldecanol, di-octyl succinate, polytrimethyleneether glycol, hexylene glycol, butoxyethyoxypropanol, n-propoxypropanol,n-butoxypropanol, diethylene glycol monobutyl ether acetate, phenylglycol ether, 2,2,4-trimethylpentanediol-1,3-monoisobutyrate, n-dibutylglutarate, n-dipentyl glutarate, n-dihexyl glutarate, n-diheptylglutarate, n-dioctyl glutarate, di-isobutyl glutarate, di-2-methylbutylglutarate, di-4-methyl-2-pentyl glutarate, di-2-ethylhexyl glutarate,pentylol glutarate, tetrapropylene glycol monobutyl ether, and the like.Mixtures of these compounds are also suitable as coalescing agents.

Coating compositions comprising the lactam-functionalized polymersaccording to the present disclosure may be applied to a variety ofsurfaces and substrates. These surfaces and substrates can include, butare not limited to, asphalt, cement, concrete, drywall, glass, masonry,metal, paper, plastic, textile, wall paper, and wood. The coatingcompositions according to the present disclosure can provide an enhancedhiding power to substrates coated with the compositions.

The polymers and their applications according to the present disclosuremay be prepared and used according to the examples set out below. Theseexamples are presented herein for purposes of illustration of thepresent disclosure and are not intended to be limiting, for example, thepreparations of the polymers and their applications.

EXAMPLES Polymer Preparation

In the examples, the following abbreviations are used:

HPP: N-(3-hydroxylpropyl)-2-pyrrolidoneHEP: N-(2-hydroxyethyl)-2-pyrrolidoneEPGE: N-[2-(2-oxiranylmethoxy)ethyl]-2-pyrrolidoneEHGE: 2-[[2-ethylhexyl)oxy]methyl]-oxiranePAPE: Polyacetal polyetherPEG1: Polyethylene glycol with approximate M_(n)=7860, M_(w)=8240PEG2: Polyethylene glycol with approximate M_(n)=8143, M_(w)=8510PEG3: Polyethylene glycol with approximate M_(n)=3640, M_(w)=3790NaOH: Sodium hydroxide

DBM: Dibromomethane

C4Br: 1-bromobutaneC8Br: 1-bromooctaneC12Br: 1-bromododecaneC16Br: 1-bromohexadecaneC18Br: 1-bromooctadecaneM_(w): Weight-average molecular weightM_(n): Number-average molecular weightM_(z): Z-average molecular weight

Example 1: Synthesis of Polymers A and B

A reactor was charged with PEG and NaOH. The temperature was adjusted toTemp1 and the contents of the reactor were stirred for 30 minutes undervacuum of 29 in. Hg. The temperature was maintained at Temp1, water wasadded, and the contents of the reactor were stirred for 30 minutes. DBMwas added and the contents of the reactor were mixed at Temp1 for 60minutes. The temperature was adjusted to Temp2 and EPGE was added. Thetemperature was then adjusted to 120° C. The contents of the reactorwere stirred for 180 minutes. The contents were discharged and allowedto cool to 20-25° C. to give Polymers A-B. Table 1 lists the reactionconditions and quantities of the reagents for making Polymers A and B.

TABLE 1 Wa- Poly- PEG PEG NaOH ter DBM EPGE Temp1 Temp2 mer Type (g) (g)(g) (g) (g) (° C.) (° C.) A PEG1 600 18.7 1.7 6.9 39.0 80 80 B PEG3 135051.9 1.0 39.9 50.0 90 90

Example 2: Synthesis of Polymers C-I

A reactor was charged with PEG and NaOH. The temperature was adjusted toTemp1 and the contents of the reactor were stirred for 30 minutes undervacuum of 29 in. Hg. The temperature was maintained at Temp1, water wasadded, and the contents of the reactor were stirred for Time1. DBM wasadded and the contents of the reactor were mixed at Temp1 for Time2. Thetemperature was adjusted to Temp2 and EPGE was added. The temperaturewas adjusted to Temp3 and the contents of the reactor were stirred atTemp3 for Time3. The temperature was adjusted to Temp4 and alkyl bromide(C4-C18 Br) was added. The temperature was then adjusted to Temp5 andthe contents of the reactor were mixed for Time4. A described polymerwas obtained except for Polymers D and E. For Polymers D and E, thecontents of the reactor were placed under vacuum at 90° C. for 50minutes. The contents were discharged and allowed to cool to 20-25° C.to give polymers C-H. Table 2 lists the reaction conditions and Table 3lists the quantities of the reagents for making Polymers C-I.

TABLE 2 Temp1 Temp2 Temp3 Temp4 Temp5 Time1 Time2 Time3 Time4 Polymer (°C.) (° C.) (° C.) (° C.) (° C.) (min) (min) (min) (min) C 80 80 90 90110 30 60 60 120 D 80 80 100 100 120 20 50 45 90 E 80 80 100 100 120 2050 45 90 F 80 80 100 100 120 30 60 60 90 G 90 120 120 120 120 30 60 15180 H 80 80 100 100 120 30 60 60 90 I 80 80 100 100 120 30 60 60 90

TABLE 3 PEG PEG NaOH Water DBM EPGE C4 Br C8 Br C12 Br C16 Br C18 BrPolymer Type (g) (g) (g) (g) (g) (g) (g) (g) (g) (g) C PEG3 1350 51.91.0 30.4 150.0 127.0 — — — — D PEG3 1350 66.7 1.0 30.4 150.0 — 162.5 — —— E PEG3 1350 66.7 1.0 30.4 90.0 — 162.5 — — — F PEG3 1080 59.4 1.6 24.3115.2 — — 74.0 — — G PEG1 600 18.7 1.7 8.0 42.9 — — 47.0 — — H PEG1 60014.0 0.4 9.1 31.6 — — — 53.0 — I PEG1 600 14.0 0.4 9.1 43.4 — — — — 57.7

Example 3: Synthesis of Polymer J

A reactor was charged with 1350 g PEG2 and 33.2 g NaOH. The temperaturewas adjusted to 90° C. and the contents of the reactor were stirred for30 minutes under vacuum of 29 in. Hg. The temperature was maintained at90° C., 0.9 g of water was added, and the contents of the reactor werestirred for 30 minutes. 7.3 g DBM was added and the contents of thereactor were mixed at 90° C. for 60 minutes. The temperature wasadjusted to 130° C. and 31.0 g EHGE was added over 60 minutes. Thecontents of the reactor were stirred at 130° C. for 120 minutes. Thetemperature was adjusted to 100° C. and 84.8 g EPGE was added. Thetemperature was then adjusted to 100° C. and the contents of the reactorwere mixed for 60 minutes. The contents were discharged and allowed tocool to 20-25° C. to give Polymer J.

TABLE 4 1st 2nd Poly- PEG PEG NaOH Water DBM DBM Temp1 Time1 mer Type(g) (g) (g) (g) (g) (° C.) (min) K PEG1 544 21.8 0.8 5.3 27.5 80 30 LPEG1 544 21.8 0.8 5.3 16.0 80 30 M PEG1 1089 43.6 1.5 10.5 69.7 120 15

Example 4: Synthesis of Polymers K-M

A reactor was charged with PEG and NaOH. The temperature was adjusted to80° C. and the contents of the reactor were stirred for 30 minutes undervacuum of 29 in. Hg. The temperature was maintained at 80° C., water wasadded, and the contents of the reactor were stirred for 30 minutes. Afirst charge of DBM was added and the contents of the reactor were mixedat 80° C. for 60 minutes. The temperature was maintained at 80° C. 15.9g HPP was added and the contents of the reactor were mixed for Time1.Then a second charge of DBM was added. The contents of the reactor werestirred at 80° C. for 60 minutes. The temperature was adjusted to Temp1.The contents were discharged and allowed to cool to 20-25° C. to givepolymers K-M. Table 4 lists the reaction conditions and the quantitiesof the reagents for making Polymers K-M.

Example 5: Synthesis of Polymer N

A reactor was charged with 1089 g PEG1 and 43.6 g NaOH. The temperaturewas adjusted to 80° C. and the contents of the reactor were stirred for30 minutes under vacuum. The temperature was maintained at 80° C., 15.9g HPP was added, and the contents of the reactor were stirred for 15minutes. The temperature was maintained at 80° C. and 69.7 g DBM wasadded. The contents of the reactor were stirred for 60 minutes. Thetemperature was adjusted to 120° C. The contents were discharged andallowed to cool to ambient temperature to give Polymer N.

Example 6: Synthesis of Polymer O

A reactor was charged with 1350 g PEG3 and 66.7 g NaOH. The temperaturewas adjusted to 90° C. and the contents of the reactor were stirred for30 minutes under vacuum of 29 in. Hg. The temperature was maintained at90° C., 1.0 g of water was added, and the contents of the reactor werestirred for 20 minutes. 30.4 g DBM was added and the contents of thereactor were mixed at 90° C. for 50 minutes. 107.5 g C8Br was added. Thetemperature was adjusted to 120° C. and the contents of the reactor werestirred for 90 minutes. The temperature was adjusted to 100° C. and150.0 g EPGE was added. The contents of the reactor were mixed for 45minutes at 100° C. The contents of the reactor were then stirred for 50minutes at 100° C. under vacuum of 29 in. Hg. The contents weredischarged and allowed to cool to 20-25° C. to give Polymer O.

Example 7: Synthesis of Polymers P

A reactor was charged with 1350 g PEG2 and 50.0 g NaOH. The temperaturewas adjusted to 90° C. and the contents of the reactor were stirred for30 minutes under vacuum of 29 in. Hg. The temperature was maintained at90° C., 2.1 g of water was added, 80.0 g HEP was added, and the contentsof the reactor were stirred at 90° C. for 60 minutes. The temperaturewas maintained at 90° C. and 49.8 g DBM was added. The contents of thereactor were stirred at 90° C. for 90 minutes. The contents of thereactor were discharged and allowed to cool to 20-25° C. to giveProphetic Polymers P.

Example 8: Synthesis of Polymer Q-T

A reactor was charged with PEG3 and NaOH. The temperature was adjustedto 90° C. and the contents of the reactor were stirred under vacuum of29 in. Hg. The temperature was maintained at 90° C., water and HEP wereadded, and the contents of the reactor were stirred at 90° C. for 60minutes. The temperature was maintained at 90° C. and DBM was added. Thecontents of the reactor were stirred at 90° C. for 90 minutes. Adescribed polymer was obtained for Polymer R. For Polymers Q, S and T,the contents of the reactor were placed under vacuum at 90° C. for 60minutes. The contents of the reactor were discharged and allowed to coolto 20-25° C. to give Prophetic Polymers Q-T. Table 5 lists the reactionconditions and the quantities of the reagents for making Polymers Q-T.

TABLE 5 PEG Polymer Type PEG (g) NaOH (g) Water (g) DBM (g) HEP (g) QPEG3 1350.0 133.5 4.7 173.8 64.5 R PEG3 1350.0 111.8 4.7 133.0 40.0 SPEG3 1350.0 111.8 4.7 173.8 96.7 T PEG3 1350.0 133.5 4.7 173.8 80.0

A reactor was charged with PEG3 and NaOH. The temperature was adjustedto 90° C. and the contents of the reactor were stirred under vacuum of29 in. Hg. The temperature was maintained at 90° C., water was added,HEP was added, and the contents of the reactor were stirred at 90° C.for 60 minutes. The temperature was maintained at 90° C. and DBM wasadded. The contents of the reactor were stirred at 90° C. for 90minutes. A described polymer was obtained for polymer R. For polymers Q,S, and T the contents of the reactor were placed under vacuum at 90° C.for 60 minutes. The contents of the reactor were discharged and allowedto cool to 20-25° C. to give Polymers Q-T.

Characterization of Polymers Polymer Purification

To a reactor were charged the prepared polymer (50.0 g) and toluene (1.0L). The reactor was purged with nitrogen and the contents of the reactorwere stirred for 45 minutes at 80° C. The reactor was cooled to 25° C.Hexane (1.0-1.5 L) was added and the resultant mixture was stirred for30 minutes at 25° C. The mixture was filtered through a sintered glassfilter funnel while the solid and hexane wet cake was stirred with aspatula. The reactor was rinsed with additional hexane (2×1.0 L). Therinsed mixture was filtered through the sintered glass filter funnelwhile the solid and hexane wet cake was stirred with a spatula. Thecollected solid was dried at 20-25° C. for 15 hours followed by dryingat 80° C. under vacuum of 29 in. Hg until constant weight was achievedto provide a purified polymer.

NMR Analysis

Sample Preparation—

Approximately 1.0 mg of tetrachloro nitrobenzene (TCNB) andapproximately 5.0 mg of polymer sample were weighed into a 1.0 mL vial.0.7 gm of CDCl₃ was added into the vial. The vial was loaded into ashaker and the shaker was operated for 30 minutes. The resultantsolution was transferred into a 5 mm NMR tube for analysis.

NMR Measurement—

Quantitative ¹H NMR spectrum was recorded using Bruker 400 MHz NMRspectrometer. Measurement parameters were as follows: temperature 300K,sweep width 20 ppm, pulse width 45 deg, number of scans 32, andrelaxation delay 25 s. Processing parameters were as follows: linebroadening 0.3 Hz. Spectrum was phase and baseline was corrected usingstandard practice. Down-field signal of residual CHCl₃ from solventCDCl₃ was referenced to 7.24 ppm.

Quantitative NMR Calculation—

EPGE weight % was calculated from the —CH₂ peaks of pyrrolidone ring (δ2.42 ppm-2.25 ppm). The weight % of hydrophobe was calculated from the—CH₂ proton that was β from the ether oxygen (—O-CH₂—CH₂—(CH₂)_(n)—CH₃,δ 1.61-1.47 ppm). The calculation was conducted based on thequantitative NMR procedure, which is described in the followingreferences: Peterson, J. ¹ H NMR analysis of mixtures using internalstandards: A quantitative experiment for the instrumental analysislaboratory, J. Chem. Educ., 1992, 69, 843-845; and Bharti, S. K. andRoy, R. Quantitative ¹ H NMR spectroscopy, Trends in AnalyticalChemistry, 2012, 35, 5-26 each publication of which is hereinincorporated in its entirety by reference.

Size Exclusion Chromatography (SEC) Measurement

SEC was used for measuring polymer molecular weight distributions.Alliance™ HPLC System and Empower™ Chromatography Data System,commercially available from the Waters Corporation (Milford, Mass.) wereused to measure the molecular weights. As used herein with respect topolymers, the terms molecular weight, average molecular weight, meanmolecular weight, and apparent molecular weight refer to the arithmeticmean of the molecular weight of individual macromolecules as measured bySEC. The relative molecular weight averages from the SEC were calculatedversus poly(ethylene glycol/ethylene oxide) (PEG/PEO) standards withnarrow molecular weight distribution.

Apparatus Set-Up—

All Waters modules in the set-up included:

Waters M515 solvent delivery systemWaters M2707 autosamplerWaters M2414 differential refractive index detector (DRI) for therelative SECColumn bank(s)—see the details in the “Analysis Conditions” sectionbelow.Waters Empower™ 3 softwareRI range 1.00 to 1.75 RIUMeasurement range 7×10⁻⁷ RIU

Drift—2×10⁻⁷ RIU

Analysis Conditions for SEC was described as follows:

Mobile Phase—70% Methanol/30% 0.6M Lithium acetate (pH 4.8) (w/w)Flow Rate—1.0 ml/miColumns—2 Shodex KW-804 Protein columns (8 mm×300 mm)+2 Shodex KW-803Protein columns (8 mm×300 mm) in series (Showa Denko America, Inc., 420Lexington Avenue, Suite 2335A, New York, N.Y. 10170, USA)

Column Temperature—40° C.

DRI (differential refractive index) Detector Temperature—40° C.Calibration—PEO/PEG standards with narrow molecular weight distribution(PSS-USA, Inc. Amherst Fields Research Park, 160 Old Farm Road, Amherst,Mass. 01002)Sample Concentration—Typically 1.5 mg/ml (unless otherwisenoted)—dissolved directly into mobile phaseInjection volume—200 μlViscosity of polymer solutions was measured using Brookfield Viscometerwith LV spindles 62, 63 or 64 at 30 rpm and 25° C. Table 6 lists theanalytical data of Polymers A-T.

TABLE 6 NMR Polymer Solution Treatment for Lactam Lactam SEC** PolymerConcentration Brookfield Polymer NMR* Hydrophobe Hydrophobe % MoietyMoiety, % Mn Mw Mz wt % Viscosity mPa · s A Purified — — EPGE 2.49 1620026600 40400 35.0 652 B Purified — — EPGE 1.35 10500 17500 26000 35.0 237C Purified n-butyl 1.27 EPGE 8.20 7860 11300 15600 35.0  94 D Purifiedn-octyl 2.37 EPGE 7.84 8200 12000 17000 35.0 203 E Purified n-octyl 2.49EPGE 5.09 8000 11300 16800 35.0 194 F Purified n-dodecyl 2.24 EPGE 6.218050 11800 16600 42.0 2220  G Purified n-dodecyl 1.60 EPGE 3.80 1930031200 46300 22.0 2440  H Purified n-hexadecyl 1.88 EPGE 3.41 23000 3940060600 20.0  2945*** I Purified n-hexadecyl 2.32 EPGE 4.47 24900 4140061800 20.0  8680*** J Purified 2-ethylhexyl 2.06 EPGE 4.08 11400 1420018200 35.0 361 K Purified — — PP 0.38 26200 48000 71500 35.0 3320  LUnpurified — — PP 0.88 27700 48600 72100 35.0 3330  M Unpurified — — PP1.12 37600 65900 94000 35.0 8900  N Unpurified — — PP 0.69 30100 5450080400 35.0 5080  O Purified n-octyl 2.48 EPGE 5.27 7010 10900 15700 35.0167 P Purified — — EP 1.06 10300 12300 15300 35.0 111 Q Unpurified — —EP 1.50 11000 18200 26200 35.0 186 R Purified — — EP 1.45 14200 2470036200 35.0 367 S Unpurified — — EP 1.88 8600 13300 18600 35.0 103 TUnpurified — — EP 1.77 9690 15600 22200 35.0 136 *The purification wasconducted according to the procedure described in “Characterization ofPolymers **SEC measurement was conducted on the unpurified samples.***1.5 wt % methyl beta cyclodextrin was used as a viscosity suppressant

Coating Applications Comparative Example

A generic semi-gloss formulation was prepared by mixing the grind andcontrol letdown formulations as shown in Table 7A and Table 7B. Thisformulation was used as a comparative standard.

Example 9—Semi-Gloss Formulation

The semi-gloss formulation was prepared by mixing Polymer F and PolymerG prepared in Example 2 with the grind and letdown formulations in Table7A and Table 7C.

TABLE 7A Grind Formulation Amount Ingredient Generic Name/Trade Name LbsGal 1 Water 71.1 8.54 2 Nuosept ™ 498G 2.00 0.21 3 Ammonium Hydroxide(28%) 1.50 0.17 4 Tamol ™ 731A 10.00 1.09 5 Dextrol ™ OC-180 HS 4.000.43 6 Drewplus ™ T-4304 3.00 0.38 7 Strodex ™ PK-95G 2.00 0.22 8Ti-Pure ™ R-706 280.00 8.41 9 Minex ® 7 30.00 1.38 10 Min-U-gel ® 4002.00 0.07 Nuosept ™ 498G: 1,2-benzisothiazolin-3-one, commerciallyavailable from Ashland Inc. Tamol ™ 731A: Sodium salt of a maleicanhydride copolymer, commercially available from The Dow ChemicalCompany. Dextrol ™ OC-180 HS: Neutralized (potassium salt) form of anethoxylated aliphatic alcohol phosphate ester, commercially availablefrom Ashland Inc. Drewplus ™ T-4304: A defoamer, commercially availablefrom Ashland Inc. Strodex ™ PK-95G: Neutralized (potassium salt) form ofa phosphate coester of aliphatic alcohols, commercially available fromAshland Inc. Ti-Pure ™ R-706: Titanium dioxide, commercially availablefrom Chemours Titanium Technologies. Minex ® 7: Micronized functionalfiller having a median particle size of 3.5 microns, commerciallyavailable from The Cary Company. Min-U-gel ® 400: A hydrous magnesiumaluminum silicate, commercially available from Active MineralsInternational, LLC.

TABLE 7B Control Letdown Formulation Amount Ingredient GenericName/Trade Name Lbs Gal 1 Rhoplex ™ VSR-1050 640.00 72.40 2 Optifilm ™Enhancer 400 8.00 0.99 3 Drewplus ™ T-4304 2.00 0.25 4 Polyphase ® 6783.00 0.32 5 Water 31.08 3.73 6 Aquaflow ™ NHS-310 12.12 1.40 7Aquaflow ™ XLS-530 0.80 0.09 Rhoplex ™ VSR-1050: Acrylic emulsion,commercially available from The Dow Chemical Company. Optifilm ™Enhancer 400: a coalescent, commercially available from Eastman ChemicalCompany. Polyphase ® 678: a fungicide, commercially available from TroyCorporation. Aquaflow ™ NHS-310: a solvent-free, nonionic syntheticassociative thickener for high shear viscosity, commercially availablefrom Ashland Inc. Aquaflow ™ XLS-530: a solvent-free, nonionic syntheticassociative thickener, commercially available from Ashland Inc.

TABLE 7C Letdown Formulation Amount Ingredient Generic Name/Trade NameLbs Gal 1 Rhoplex ™ VSR-1050 640.00 72.40 2 Optifilm ™ Enhancer 400 8.000.99 3 Drewplus ™ T-4304 2.00 0.25 4 Polyphase ® 678 3.00 0.31 5 Water31.20 3.75 6 Polymer F 10.20 1.18 7 Polymer G 2.60 0.30 Rhoplex ™VSR-1050: Acrylic emulsion, commercially available from The Dow ChemicalCompany. Optifilm ™ Enhancer 400: a coalescent, commercially availablefrom Eastman Chemical Company. Polyphase ® 678: a fungicide,commercially available from Troy Corporation.

Performance of Coatings

Consistency of coating compositions was evaluated by measuring the KrebsUnit (KU) viscosity using a Stormer-Type Viscometer as per the standardtest method ASTM D562. High-shear (ICI) viscosity of compositions wasevaluated using a Cone/Plate Viscometer as per the standard test methodASTM D4287. Sag was measured based on the standard ASTM D4400 Method.Levelling was measured based on the standard ASTM D4062 Method.

Applied hide was evaluated by the following general method: The paintformulations prepared in Comparative Example and Example 9 were stirredfor approximately 5-10 times. Next, approximately 300-400 g of the paintformulation was poured into a standard 11-inch paint tray. A 7 inch or9-inch roller was then rolled into the tray for wetting out andconditioning the roller cover. The roller was then primed on a scrappiece of drywall with 5 full vertical strokes. The roller was thenreturned to the tray and rolled another 3-5 times. The tray containingthe roller was then placed on a balance and zeroed. Paint was thenapplied to a CU-1M chart in a uniform manner until the CU-1M chart wasappropriately covered. The roller was then placed back into the tray andthe amount of paint applied was recorded. Paints were reapplied if thefinal spread rates of the paints to be compared were not within 50 sq.ft. of each other. The CU-1M charts were dried for 24 hours at 25° C.CU-1M charts were then evaluated visually for the applied hide with 10equaling the best and 1 equaling the worst. The results are listed inTable 8.

The data shows different sag, leveling characteristics, and applied hideof paints formulated to similar KU and ICI viscosity values. It isevident that the formulation comprising the polymers of the presentdisclosure performs better than the comparative standard.

TABLE 8 Applied Hide on CU-1M Leneta Sag Chart Resistance Leneta (RatingLow Shear High Shear Rating Leveling 1-10; KU ICI Thickening Thickening4-24 Rating 1-9 1 = worst, Formulation Viscosity Viscosity EfficiencyEfficiency (*= no drip) (9 = best) 10 = best) Comparative 102 1.38 0.010.22 18* 8 7 Example Example 9 100 1.47 0.05 0.20 12* 9 10 Thickeningefficiency = [[Weight of Polymer (g)] × [100]]/[Weight Final Paint (g)]

What is claimed is:
 1. A lactam-functionalized polymer comprising: apolymer backbone and at least one lactam-containing moiety attached tothe polymer backbone, wherein the polymer backbone is selected from thegroup consisting of polyacetal polyether, polyhemiaminal polyether,polyaminal polyether, and combinations thereof.
 2. Thelactam-functionalized polymer of claim 1, wherein the at least onelactam-containing moiety is attached to at least one end of the polymerbackbone or pendant on the polymer backbone.
 3. Thelactam-functionalized polymer of claim 2, wherein the at least onelactam-containing moiety has a general formula (I):

wherein R is a substituted or unsubstituted hydrocarbon diradicaloptionally having at least one heteroatom and is attached to a carbon ornitrogen atom on the lactam ring, and b is from 1 to
 5. 4. Thelactam-functionalized polymer of claim 2, wherein the at least onelactam-containing moiety has a general formula (II):

wherein R′ and R″ are identical or different and are each independentlyhydrogen or a substituted or unsubstituted hydrocarbon diradicaloptionally having at least one heteroatom, and R″ is attached to acarbon atom on the lactam ring, and b is from 1 to 5 with the provisothat R′ or R″ or both R′ and R″ are a substituted or unsubstitutedhydrocarbon diradical optionally having at least one heteroatom.
 5. Thelactam-functionalized polymer of claim 3, wherein R is selected from thegroup consisting of a substituted or unsubstituted alkylene, alkenyl,aryl, alkylaryl, arylalkylene, arylalkenyl, cyclic, cycloaliphatic andpolycyclic, optionally having at least one heteroatom.
 6. Thelactam-functionalized polymer of claim 4, wherein R′ and R″ areidentical or different and are each independently selected from thegroup consisting of a substituted or unsubstituted alkylene, alkenyl,aryl, alkylaryl, arylalkylene, arylalkenyl, cyclic, cycloaliphatic andpolycyclic, optionally having at least one heteroatom.
 7. Thelactam-functionalized polymer of claim 5, wherein R is an alkylenehaving 1 to 30 carbon atoms, optionally having at least one heteroatom.8. The lactam-functionalized polymer of claim 6, wherein R′ and R″ areidentical or different and are each independently an alkylene having 1to 30 carbon atoms, optionally having at least one heteroatom.
 9. Thelactam-functionalized polymer of claim 3, wherein the at least onelactam-containing moiety has one or both of the following generalformulas:

wherein L is a direct bond, or a substituted or unsubstituted alkyleneoptionally having at least one heteroatom; A is hydrogen, OX_(n)H,SX_(n) H, or NR₄X_(n)H; R₁-R₄ are identical or different and are eachindependently hydrogen, linear or branched alkyl having 1 to 30 carbons,or saturated or unsaturated hydrocarbon rings having 3 to 10 carbons,optionally having at least one heteroatom; X is the lactam-containingmoiety of Formula (III) or (IV); n is from 0 to 500; and b is from 1 to5.
 10. The lactam-functionalized polymer of claim 4, wherein R′ and R″are identical or different and are each independently hydrogen,

wherein L is attached to the lactam ring, and is a direct bond, or asubstituted or unsubstituted alkylene optionally having at least oneheteroatom; A is hydrogen, OX_(n)H, SX_(n) H, or NR₄X_(n)H; R₁-R₄ areidentical or different and are each independently hydrogen, linear orbranched alkyl having 1 to 30 carbons, or saturated or unsaturatedhydrocarbon rings having 3 to 10 carbons, optionally having at least oneheteroatom; X is the lactam-containing moiety of Formula (II); n is from0 to 500; and b is from 1 to 5 with the proviso that R′ or R″ or both R′and R″ are a substituted or unsubstituted hydrocarbon diradicaloptionally having at least one heteroatom.
 11. The lactam-functionalizedpolymer of claim 1, wherein the polymer further comprises at least onehydrophobic moiety to form a hydrophobically modifiedlactam-functionalized polymer.
 12. The lactam-functionalized polymer ofclaim 11, wherein the hydrophobically modified lactam-functionalizedpolymer comprises at least one hydrophobic moiety attached to at leastone end of the lactam-functionalized polymer or pendant on thelactam-functionalized polymer.
 13. The lactam-functionalized polymer ofclaim 12, wherein the at least one hydrophobic moiety is selected fromthe group consisting of substituted or unsubstituted alkyl, alkenyl,aryl, alkylaryl, arylalkyl, arylalkenyl, cyclic, cycloaliphatic, andpolycyclic, optionally having at least one heteroatom.
 14. Thelactam-functionalized polymer of claim 1, wherein the number of the atleast one lactam-containing moiety is from 1 to
 500. 15. Thelactam-functionalized polymer of claim 11, wherein the number of the atleast one hydrophobic moiety is from 1 to
 500. 16. A method forpreparing a lactam-functionalized polymer comprising: 1) reacting ahydroxyl polyether or hydroxyl polyetheramine with a gem-dihalide toform a polymer backbone; and 2) reacting the polymer backbone with atleast one compound comprising at least one lactam moiety to form thelactam-functionalized polymer.
 17. The method of claim 16, wherein theat least one compound further comprises at least one reactive functionalgroup.
 18. The method of claim 17, wherein the at least one compound hasa general formula (V):

where Y is Cl, Br, I, F, OH, SH, or NR₇R₈; R₅ and R₆ are identical ordifferent and are each independently hydrogen, Cl, Br, I, F, OH, SH,NR₇R₈, linear or branched alkyl having 1 to 30 carbons, or saturated orunsaturated hydrocarbon rings having 3 to 10 carbons, optionally havingat least one heteroatom; R₇ and R₈ are identical or different and areeach independently hydrogen, linear or branched alkyl having 1 to 30carbons, or saturated or unsaturated hydrocarbon rings having 3 to 10carbons, optionally having at least one heteroatom; a is from 1 to 20 orfrom 1 to 8; and b is from 1 to
 5. 19. The method of claim 17, whereinthe at least one compound has a general formula (VI):

wherein W and W′ are identical or different and are each independentlyhydrogen or

wherein Y is Cl, Br, I, F, OH, SH, or NR₇R₈; R₅ and R₆ are identical ordifferent and are each independently hydrogen, Cl, Br, I, F, OH, SH,NR₇R₈, linear or branched alkyl having 1 to 30 carbons, or saturated orunsaturated hydrocarbon rings having 3 to 10 carbons, optionally havingat least one heteroatom; R₇ and R₈ are identical or different and areeach independently hydrogen, linear or branched alkyl having 1 to 30carbons, or saturated or unsaturated hydrocarbon rings having 3 to 10carbons, optionally having at least one heteroatom; a is from 1 to 20 orfrom 1 to 8; and b is from 1 to 5 with the proviso that W or W′ or bothW and W′ are a substituted or unsubstituted hydrocarbon diradicaloptionally having at least one heteroatom.
 20. The method of claim 17,wherein the at least one compound has a general formula (VII):

wherein Y is O, S, or NR₇; Z is O, S, or NR₇; R₅ and R₆ are identical ordifferent and are each independently hydrogen, Cl, Br, I, F, OH, SH,NR₇R₈, linear or branched alkyl having 1 to 30 carbons, or saturated orunsaturated hydrocarbon rings having 3 to 10 carbons, optionally havingat least one heteroatom; R₇ and R₈ are identical or different and areeach independently hydrogen, linear or branched alkyl having 1 to 30carbons, or saturated or unsaturated hydrocarbon rings having 3 to 10carbons, optionally having at least one heteroatom; a is from 1 to 20 orfrom 1 to 8; and b is from 1 to
 5. 21. The method of claim 17, whereinthe at least one compound has a general formula (VIII):

wherein V and V′ are identical or different and are each independentlyhydrogen or

wherein Y is O, S, or NR₇; Z is O, S, or NR₇; R₅ and R₆ are identical ordifferent and are each independently hydrogen, Cl, Br, I, F, OH, SH,NR₇R₈, linear or branched alkyl having 1 to 30 carbons, or saturated orunsaturated hydrocarbon rings having 3 to 10 carbons, optionally havingat least one heteroatom; R₇ and R₈ are identical or different and areeach independently hydrogen, linear or branched alkyl having 1 to 30carbons, or saturated or unsaturated hydrocarbon rings having 3 to 10carbons, optionally having at least one heteroatom; a is from 1 to 20 orfrom 1 to 8; and b is from 1 to 5 with the proviso that V or V′ or bothV and V′ are a substituted or unsubstituted hydrocarbon diradicaloptionally having at least one heteroatom.
 22. The method of claim 16,wherein the lactam-functionalized polymer further reacts with at leastone compound comprising at least one hydrophobic moiety.